US5108974A - Preparation of vanadium-phosophorus-oxide catalyst precursor - Google Patents
Preparation of vanadium-phosophorus-oxide catalyst precursor Download PDFInfo
- Publication number
- US5108974A US5108974A US07/630,128 US63012890A US5108974A US 5108974 A US5108974 A US 5108974A US 63012890 A US63012890 A US 63012890A US 5108974 A US5108974 A US 5108974A
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- vanadium
- phosphoric acid
- catalyst precursor
- oxide catalyst
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- 239000012018 catalyst precursor Substances 0.000 title claims abstract description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 12
- -1 alkyl silicate Chemical compound 0.000 claims abstract description 7
- LJYCJDQBTIMDPJ-UHFFFAOYSA-N [P]=O.[V] Chemical compound [P]=O.[V] LJYCJDQBTIMDPJ-UHFFFAOYSA-N 0.000 claims abstract description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 abstract description 12
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 abstract description 12
- 238000002441 X-ray diffraction Methods 0.000 abstract description 4
- 235000019445 benzyl alcohol Nutrition 0.000 abstract description 4
- 239000003638 chemical reducing agent Substances 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- LOUBVQKDBZRZNQ-UHFFFAOYSA-M [O-2].[O-2].[OH-].O.[V+5] Chemical compound [O-2].[O-2].[OH-].O.[V+5] LOUBVQKDBZRZNQ-UHFFFAOYSA-M 0.000 description 3
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 2
- JKJKPRIBNYTIFH-UHFFFAOYSA-N phosphanylidynevanadium Chemical compound [V]#P JKJKPRIBNYTIFH-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- AFLKKLSCQQGOEK-UHFFFAOYSA-N 3-methyl-1-phenylbutan-2-ol Chemical compound CC(C)C(O)CC1=CC=CC=C1 AFLKKLSCQQGOEK-UHFFFAOYSA-N 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- GLMOMDXKLRBTDY-UHFFFAOYSA-A [V+5].[V+5].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical class [V+5].[V+5].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GLMOMDXKLRBTDY-UHFFFAOYSA-A 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 208000018747 cerebellar ataxia with neuropathy and bilateral vestibular areflexia syndrome Diseases 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000012002 vanadium phosphate Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/215—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Definitions
- VPO vanadium-phosphorus-oxide
- the VPO catalyst precursor is ordinarily prepared by reducing vanadium pentoxide to vanadium tetraoxide with benzyl alcohol in an isobutanol solution.
- the benzyl alcohol is oxidized to benzaldehyde.
- the vanadium tetraoxide is then reacted with phosphoric acid in the presence of tetraethylorthosilicate to form the desired precursor phase having the formula (VO) 2 H 4 P 2 O 9 .
- U.S. Pat. No. 4,632,916, at Col. 4, lines 1-6 indicates that various reductants can be employed including isobutanol, benzyl alcohol, and "reduced acids of phosphorus like H 3 PO 3 .
- the isobutanol is oxidized more slowly to isobutyraldehyde, and butyral.
- the foregoing procedure can be varied without using benzyl alcohol as the reductant if the vanadium pentoxide is reduced to the desired vanadium tetraoxide by being heated in the presence of a mixture of an alcohol and sufficient phosphoric acid. Even though the reduction of the pentoxide to the tetraoxide is achieved, the catalyst precursor that is precipitated in this system will not be crystalline (VO) 2 H 4 P 2 O 9 unless an alkyl silicate is present. When this specific compound is formed, rather than mixed vanadium phosphates, catalysts made from it give butane to maleic anhydride yields of up to about 90%, rather than 50% to 60%.
- the reduction of the vanadium pentoxide is accomplished in accordance with the instant invention by heating the pentoxide in an appropriate solvent such as an alcohol, e.g., isobutanol, in the presence of a mixture of tetraethylorthosilicate and phosphoric acid.
- an appropriate solvent such as an alcohol, e.g., isobutanol
- the vanadium pentoxide is preferably in milled form, and the amount of phosphoric acid used should be sufficient (when taken with the later added amount of phosphoric) to give a P/V ratio in the final catalyst of from about 0.9:1 to about 1.3:1.0 as mentioned at Col. 4, lines 21-33, of U.S. Pat. No. 4,632,916.
- the mixture of vanadium pentoxide, solvent, phosphoric acid, and tetraethylorthosilicate is preferably heated to reflux to achieve the desired degree of reduction.
- V 2 O 5 Approximately 7 lbs of V 2 O 5 were finely ground through a model JT-6 Fitz mill using a 325 mesh screen with a canvass sock. The milling took place over a period of approximately 15 minutes and the V 2 O 5 was fed slowly with dry ice.
- the resulting mixture was heated to reflux (about 100C) for approximately 13 hours. Then, the remainder of the 85% phosphoric acid (206 gm) was added. The resulting mixture was refluxed for 6-7 hours with a blue-green precipitate forming during this step.
- the resulting reaction mixture was cooled down to close to room temperature and filtered through a 10-15 micron fritted glass filter with vacuum.
- the product retained by the filter was washed twice with 250 ml of isobutanol and was dried in an oven at 145C and vacuum (20 mm Hg) for eight hours.
- the product weighed about 490 gm and it was passed through a 100 mesh screen to form a more uniform particle size.
- the product was confirmed by X-ray diffraction to be a (VO) 2 H 4 P 2 O 9 catalyst precursor for a vanadium-phosphorus mixed oxide catalyst.
- Example 1 A series of variations were made in the procedure of Example 1 where certain reagents were either present or absent or were changed in some manner.
- the X-ray diffraction pattern of the resulting product either conformed to that of (VO) 2 H 4 P 2 O 9 ("OK”) or did not ("NG").
Abstract
Vanadium pentoxide can be reduced to the +4 oxidation state from the +5 state, in the manufacture of vanadium-phosphorus-oxide catalyst precursor, (VO)2 H4 P2 O9, by using phosphoric acid as the reducing agent rather than benzyl alcohol. Use of an alkyl silicate with the phosphoric acid insures the correct crystalline species, (VO)2 H4 P2 O9, as indicated by X-ray diffraction.
Description
It is well known in the art to synthesize vanadium-phosphorus-oxide (VPO) catalysts for the selective oxidation of C4 hydrocarbons to maleic anhydride. A recent article which affords an overview of this area of technology is H. S. Horowitz et al., Applied Catalysis, 38 (1988) 193-210 and U.S. Pat. No. 4,677,084 to H. E. Bergna which are each incorporated herein in their entirety.
The VPO catalyst precursor is ordinarily prepared by reducing vanadium pentoxide to vanadium tetraoxide with benzyl alcohol in an isobutanol solution. The benzyl alcohol is oxidized to benzaldehyde. The vanadium tetraoxide is then reacted with phosphoric acid in the presence of tetraethylorthosilicate to form the desired precursor phase having the formula (VO)2 H4 P2 O9. U.S. Pat. No. 4,632,916, at Col. 4, lines 1-6 indicates that various reductants can be employed including isobutanol, benzyl alcohol, and "reduced acids of phosphorus like H3 PO3. In the case of using isobutanol and benzyl alcohol, the isobutanol is oxidized more slowly to isobutyraldehyde, and butyral.
The foregoing procedure can be varied without using benzyl alcohol as the reductant if the vanadium pentoxide is reduced to the desired vanadium tetraoxide by being heated in the presence of a mixture of an alcohol and sufficient phosphoric acid. Even though the reduction of the pentoxide to the tetraoxide is achieved, the catalyst precursor that is precipitated in this system will not be crystalline (VO)2 H4 P2 O9 unless an alkyl silicate is present. When this specific compound is formed, rather than mixed vanadium phosphates, catalysts made from it give butane to maleic anhydride yields of up to about 90%, rather than 50% to 60%.
The reduction of the vanadium pentoxide is accomplished in accordance with the instant invention by heating the pentoxide in an appropriate solvent such as an alcohol, e.g., isobutanol, in the presence of a mixture of tetraethylorthosilicate and phosphoric acid. The vanadium pentoxide is preferably in milled form, and the amount of phosphoric acid used should be sufficient (when taken with the later added amount of phosphoric) to give a P/V ratio in the final catalyst of from about 0.9:1 to about 1.3:1.0 as mentioned at Col. 4, lines 21-33, of U.S. Pat. No. 4,632,916. The mixture of vanadium pentoxide, solvent, phosphoric acid, and tetraethylorthosilicate is preferably heated to reflux to achieve the desired degree of reduction.
Then, additional phosphoric acid is added (to achieve the above-stated P/V ratio in the final catalyst) followed by additional refluxing to precipitate the desired crystalline (VO)2 H4 P2 O9 catalyst precursor for a vanadium-phosphorus mixed oxide catalyst.
The Examples which follow set forth in more detail a various embodiments of the claimed invention.
Approximately 7 lbs of V2 O5 were finely ground through a model JT-6 Fitz mill using a 325 mesh screen with a canvass sock. The milling took place over a period of approximately 15 minutes and the V2 O5 was fed slowly with dry ice.
A 5 liter flask equipped with a heating mantle with variac, stirrer, and reflux condenser was charged with the following ingredients:
______________________________________ Ingredient Weight (grams) ______________________________________ Isobutanol 2004 V.sub.2 O.sub.5 (air-dried) 250 Tetraethylorthosilicate 305 Phosphoric Acid (85%) 160 ______________________________________
The resulting mixture was heated to reflux (about 100C) for approximately 13 hours. Then, the remainder of the 85% phosphoric acid (206 gm) was added. The resulting mixture was refluxed for 6-7 hours with a blue-green precipitate forming during this step.
The resulting reaction mixture was cooled down to close to room temperature and filtered through a 10-15 micron fritted glass filter with vacuum. The product retained by the filter was washed twice with 250 ml of isobutanol and was dried in an oven at 145C and vacuum (20 mm Hg) for eight hours. The product weighed about 490 gm and it was passed through a 100 mesh screen to form a more uniform particle size. The product was confirmed by X-ray diffraction to be a (VO)2 H4 P2 O9 catalyst precursor for a vanadium-phosphorus mixed oxide catalyst. The X-ray diffraction peaks for (VO)2 H4 P2 O9 and their relative intensity (100 =the height of the most intense peak) were:
______________________________________ 20 Rel. Intensity ______________________________________ 30.347 100 15.481 68 26.998 60 19.604 43 24.098 38 28.736 26 31.982 23 33.667 21 14.940 19 33.409 15 37.328 15 34.142 14 39.912 9 37.136 7 36.775 7 35.022 6 37.637 6 34.784 5 36.403 5 39.620 4 ______________________________________
A series of variations were made in the procedure of Example 1 where certain reagents were either present or absent or were changed in some manner. The X-ray diffraction pattern of the resulting product either conformed to that of (VO)2 H4 P2 O9 ("OK") or did not ("NG").
______________________________________ benzyl i-butanol alcohol TEOS V.sub.2 O.sub.5 H.sub.3 PO.sub.4 (85%) XRD 500 ml (50 ml) (61 g) (50 g) 75 g Data ______________________________________ Yes Yes Yes Yes Yes OK Yes No Yes Yes NH.sub.4 CO.sub.3 NG Yes No Yes Yes 1 gm OK Yes Yes Yes 200 gm Yes OK Yes Yes Yes Yes Yes OK Yes Yes Yes Yes Yes OK Yes Yes Yes Yes Yes OK Yes No Yes Yes Yes OK Yes Yes Yes Yes Yes OK Yes No Yes Yes Yes OK Yes No No Yes 100% NG Yes Yes No Yes 100% NG 2500 ml 250 ml 305 ml 250 ml 375 g OK 2500 ml No 305 ml 250 ml 375 g OK Yes No No Yes 100% NG Yes No ethanol Yes 100% NG Yes Yes No Yes 100% NG Yes No Yes Yes Yes OK Yes Yes Yes Yes Yes OK Yes No Yes Yes Yes OK ______________________________________
Claims (4)
1. A process for forming the vanadium-phosphorus-oxide catalyst precursor (VO)2 H4 P2 O9 which comprises reducing milled V2 O5 to V2 O4 by heating the V2 O5 in the presence of an alcohol, an alkyl silicate, and phosphoric acid and precipitating the product with additional phosphoric acid in the presence of the alkyl silicate.
2. A process as claimed in claim 1 wherein at least about 80% of the milled V2 O5 is less than 325 mesh.
3. A process as claimed in claim 1 wherein the alkyl silicate is ethyl silicate.
4. A process as claimed in claim 1 wherein at least 80% of the milled V2 O5 is less than 325 mesh and the alkyl silicate is ethyl silicate.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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US07/630,128 US5108974A (en) | 1990-12-19 | 1990-12-19 | Preparation of vanadium-phosophorus-oxide catalyst precursor |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US07/630,128 US5108974A (en) | 1990-12-19 | 1990-12-19 | Preparation of vanadium-phosophorus-oxide catalyst precursor |
Publications (1)
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US5108974A true US5108974A (en) | 1992-04-28 |
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US07/630,128 Expired - Fee Related US5108974A (en) | 1990-12-19 | 1990-12-19 | Preparation of vanadium-phosophorus-oxide catalyst precursor |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1082941C (en) * | 1993-12-22 | 2002-04-17 | 三菱化学株式会社 | Process for producing a phosphours-vanadium oxide catalyst precursor, process for producing a phosphorus-vanadium oxide catalyst, and process for producing maleic anhydride by vapor phase oxidation... |
WO2004067170A1 (en) * | 2003-01-30 | 2004-08-12 | New Tianjin T. & D. Co., Ltd | V-p-ci composite oxide catalyst precursor used for producing maleic anhydride from butance |
WO2004080131A1 (en) * | 2003-03-05 | 2004-09-16 | Alexei Dmitrievich Kanareikin | Charge particle beam accelerator |
US20060198776A1 (en) * | 2005-03-03 | 2006-09-07 | Cross Joseph B | Mercury removal sorbent |
CN106000434A (en) * | 2016-05-23 | 2016-10-12 | 刘阳 | Maleic anhydride catalyst and preparation method thereof |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4062873A (en) * | 1974-12-23 | 1977-12-13 | Chevron Research Company | Producing maleic anhydride using certain phosphorous-vanadium-silicon-oxygen containing catalysts |
US4382876A (en) * | 1980-03-20 | 1983-05-10 | Kurt Neubold | Method for producing catalysts for gas phase oxidation of saturated and/or unsaturated C4 -hydrocarbons to maleic anhydride |
US4632916A (en) * | 1985-07-15 | 1986-12-30 | E. I. Du Pont De Nemours And Company | Fumed silica modified catalyst |
US4677084A (en) * | 1985-11-27 | 1987-06-30 | E. I. Du Pont De Nemours And Company | Attrition resistant catalysts, catalyst precursors and catalyst supports and process for preparing same |
-
1990
- 1990-12-19 US US07/630,128 patent/US5108974A/en not_active Expired - Fee Related
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4062873A (en) * | 1974-12-23 | 1977-12-13 | Chevron Research Company | Producing maleic anhydride using certain phosphorous-vanadium-silicon-oxygen containing catalysts |
US4064070A (en) * | 1974-12-23 | 1977-12-20 | Chevron Research Company | Catalyst for producing maleic anhydride |
US4382876A (en) * | 1980-03-20 | 1983-05-10 | Kurt Neubold | Method for producing catalysts for gas phase oxidation of saturated and/or unsaturated C4 -hydrocarbons to maleic anhydride |
US4632916A (en) * | 1985-07-15 | 1986-12-30 | E. I. Du Pont De Nemours And Company | Fumed silica modified catalyst |
US4677084A (en) * | 1985-11-27 | 1987-06-30 | E. I. Du Pont De Nemours And Company | Attrition resistant catalysts, catalyst precursors and catalyst supports and process for preparing same |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1082941C (en) * | 1993-12-22 | 2002-04-17 | 三菱化学株式会社 | Process for producing a phosphours-vanadium oxide catalyst precursor, process for producing a phosphorus-vanadium oxide catalyst, and process for producing maleic anhydride by vapor phase oxidation... |
WO2004067170A1 (en) * | 2003-01-30 | 2004-08-12 | New Tianjin T. & D. Co., Ltd | V-p-ci composite oxide catalyst precursor used for producing maleic anhydride from butance |
US20060241310A1 (en) * | 2003-01-30 | 2006-10-26 | Renshui Lan | V-p-ci composite oxide catalyst precursor used for producing maleic anhydride from butance |
US7547655B2 (en) * | 2003-01-30 | 2009-06-16 | New Tianjin T. & D. Co., Ltd. | V-P-Si composite oxide catalyst precursor used for producing maleic anhydride from butance |
WO2004080131A1 (en) * | 2003-03-05 | 2004-09-16 | Alexei Dmitrievich Kanareikin | Charge particle beam accelerator |
US20060198776A1 (en) * | 2005-03-03 | 2006-09-07 | Cross Joseph B | Mercury removal sorbent |
CN106000434A (en) * | 2016-05-23 | 2016-10-12 | 刘阳 | Maleic anhydride catalyst and preparation method thereof |
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